1-alkyl-3-acylamido-5-pyrazolone couplers for color photography



1"ALKYL'3'ACYLAMIDOF5PYRAZOLQNE CQU- PLERS F OR COLOR PHOTOGRABHY George Feniak, Anthony Loria, and Warren A. Reckhow,

ttes Patent O Rochester, N. Y., ass'ignors to Eastman Kodak Cornpany, Rochester, N.'Y., a corporation of New Jersey No Drawing. Application September 18, 1956 Serial'No; 610,639

4 Claims. .(Cl. 96-94) This invention relates to 1-alkyl-3-acylamido 5-pyrazolone couplers for color photography and more particularly to such couplers in which the 3-acylamido gronp is a 3-phenoxyacylamido group and which substituents in the 1 and 3-positions of the pyrazolone nucleus confer special properties upon the coupler compounds.

S-acyIamidQ-S-pyra-Zolone couplers for color photography have previously been described includingalimited number of 1-alkyl-3-acylamido-5-pyrazolones. However, the pyrazolone coupler compounds of the present invention are distinguished in containing a particular combination of alkyl and acylamido radicals in the 1 and 3.-po.sitions of the pyrazolone nucleus with the result that-dyes obtained from the couplers in the color development proc- C Ha-N 2 Clix-P g 2,865,751 Patented p p! wherein R represents an alkyl group of from 1 to 12 carbon a om Rire e e ts a pn s a l p the benzene series such as phenyl and substituted phenyl, for example, 2,4-di-tert.-amylphenyl, 2,4-di-n-amylphenyl, n represents a positive integer of from Ito. 2, and n' represents a positive integer of from 1 to 3, R represents a hydrogen atom or lower alkyl group and m represents a positive integer from 1 to 2.

Representative couplers of the invention having the above generalstructure are as follows: i

No. 1 A max. 520

No. 2 A max..520

'I-methyl-SIa-M-[a- (2 4-di-tert-amylphnoxy) acetainldol p len sslacetami l fi p m l n No. 3 A max. 524

O O --NH- (CHDfiONH-ii-GHPOQCilia) IHMt) e hr -tv-( rt 2 omi v nhe i xmasetamm l phenoxy}butyramldoII-B-pyrazolone ims -).max. 523

No.4 at max. 524

, i dodecyl-ti-[a' (2,4-ditert.-amylphenoxy) acetamidol'fi- Q pyrazolone No.6 Kmart. 522

Odin- (EsHu (n) 1-dodecyl-3-[a-(2,4-dt-n-amylphenoxy)acetamldol-S-pyrazolone No.8 IBEX-523 0 NHC 1-dodecyl-3-(m-[a-(flA-fii-n-nrhylphenoxy)ncetamido] 1 benzamido}-5-pyrazolone Ca as-N;

The A max. values indicated represent the wavelength of maximum light absorption of dyes made by oxidative coupling of each coupler with the developing agent 2- amino-S-diethylamino toluene hydrochloride.

The coupler compounds of the invention can be prepared in the following manner: 1

l METHYL 1 3 (a (4 NITROPHENOXXUACET- AMIDO) 5 PYRAZOLONE Calc. for Found, Analysts (GnHnNrOa). percent percent 4 l METHYL 3 (u (4 AMINOPHENOXY) ACET- AMIDO) 5 PYRAZOLONE I-methyl-3-(a-(4-nitrophenoxy) acetamido)-5-pyrazolone, 7 g. (.029 mole) was charged in a pressure bottle with 250 ml. of ethyl alcohol, 100 ml. of water and about 0.5 g. of nickel catalyst and the bottle shaken under lbs. of hydrogen pressure for 1 hr. at 70-80 C. The mixture was filtered and the solvent evaporated under reduced pressure on a steam bath. The residue was dissolved in hot water, filtered and the filtrate cooled to 0 C. The precipitate which formed was filtered washed with 20 ml. of ice water and air dried. I a

Yield 4.1g. of white plates M. P. 100-102 C.

calmer "Found, Analysts (CnHuMOs), percent 7 i percent N 21.4 21.6

Coupler N0. 1

l-rnethyl-3-[a-(4-aminophenoxy) acetamido1-5-pyrazolone 2 g. (.0076 mole) and a-(ZA-di-tert. amylphenoxy) butyryl chloride 5 g. (.015 mole) were mixed in 50 ml. of dry acetonitrile and 2 ml. of pyridine were added. After stirring the mixture for 30 min., the gum which had separated out was brought back in solution by the addition of 2g. of KOI-l and 50 ml. of ethyl alcohol. After 15 min. the solution was acidified with acetic acid and the precipitate which formed on adding water (50 ml.) was filtered, washed with water and dried.

The product was obtained from petroleum ether as a white powder. Yield 2.5 g. M. P. 78-80 C.

Calc. for Found, (CMH MOs) percent percent Analysis wow-- Coupler N0. 2

Found, percent Coupler No. 3

A mixture of the sodium salt of p-nitrophenol (322 g.) 'y-chlorobutyronitrile (207 g.), n-propanol (3 l.) and water (1 l.) was refluxed for hours. The mixture was distilled until 2 liters of distillate was collected and the residue was poured into water (4 1.). The solid was filtered otf, washed well with water and recrystallized twice from ethyl alcohol. It melted at 53-4 C. This material was hydrolyzed to 'y-(p-nitrophenoxy) butyric acid by heating it with a 3 to 1 mixture of glacial acetic 5. acid'and concentrated hydrochloricacid'overnight'on a steam bath. When the reaction mixture was-cooled, the product crystallized (M. P'. 127'-8C.'). This acid was converted to the acid chloride with thionyl chloride'underthe usual conditions. The acidchloride melted at 56-7 C.

v-(p-nitrophenoxy) butyryl chloride- (4.1 g.), which was preparedabove, was added to a-=refluxing solution 'of. 1 rnethyl 3 amino-S-pyrazolone (2.5 g:) in dry aeetonitrile' (100 ml.). After 5 minutes, pyridine (2-ml.)'was=added. and the refluxing was continued for an additional 30 minutes. The reactionmixture was= drowned" out in water. The resulting solid i was filtered off," washed with water, dried and recrystallized from-absolute -ethanol. It melted at 198-203 C. This material was reducedover Raney nickel in absoluteethanolatSO CL With hydrogen at a pressure-of'20 lbs: per 'sqain. Theethanolic solution of 1-methyl-3-['y-(p-aminophenoxy) bntyramido1-5- pyrazolone thusaobtained was concentrated to dryness and the residue wasarecrystallized"from water (M. P: 140-2 C.). The productwas condensed with 2 equivalentsof 2,4-di-tert.-amylphenoxyacetal chloride in the presence of 2 equivalents of pyridine in dry acetonitrile at30 C. for 30 minutes. The reaction mixture was drowned-out in water and the diacyl compound was hydrolyzed with 2 equivalents ofialcoholicv potassium 'hydroxideat room tema perature for 30- minutes; When therreactionsmixture was acidified withacetic acid, thelproduct separated asan oil. Thiswas washed with water, vvarmed with ether, ,filteredl and. recrystallized from benzene; Ittmelted-at:135'-7. Anal. calcd..for"C H N O C, 68.1; H, 7.8; N, 9 .9.- Found: C, 68.3; H, 7.9; N, 10.0.

Coupler N0. 4

A mixture of l-chlorododecane (400 g.), ethyl alcohol- (1840 ml.) and 95% aqueous.hydrazine (340 g.) was heated" to reflux for 18 hours. The ethanol was distilledofi under reduced pressure (20 mm.) and the residuewasextracted with ether (3 1.). The ether extractswere dried and distilled. The fraction distilling. at 154-'-8 Cat 1 mm. pressure was collected. A mixture of the dodecyl hydrazine (184 g.) obtained above, ethyl fiL-ethoxyfi-amino acrylate (160 g.) and. absolute ethanol (920' g.'-) 'waszallowedto standatroom temperature for 5 hours; then heatedLtov reflux for 30 minutes and cooledto 'O C. The 1-dodecyl-3-amino-5pyrazolone was: filtered 01f and. recrystallized twice from absolute ethanol. It'meltedrat 77.5-78.5 C. This material was:treated.with; 2-fequiv= alentsof 2,4-di=tert.-amylphenoxyacetyl i chloride and. 2 equivalents of T N',N-dimethylaniline in refiuxingracetonitrile fr;3 /z hours. Thereaction mixturerwassdrowned out in water. The diacylatedzcomp'ound was hydrolyzed with 2 equivalents of sodium hydroxideirr aqueous :ethanol. at room temperature for 30 minutes. The reaction mixture was acidified with acetic acid, the solid product was filtered off, recrystallized from ethanol and then benzene (M. P. 78-80 C.). Anal. calcd; for C H N O C, 73.1; H, 10.2; N, 7.8. Found: C, 73.5; H, 10.3; N, 8.1.

Coupler No..

coupler 2 except that 1-hexyl-3-amino-5-pyrazolone was used' in place of 1-methyl-3 amino 5 pyrazolone: It'

Coupler No; 7 Coupler-Twas. prepared.-in. the same manner as was coupler 4 except that 2,4-di-n-amylphenoxyacetyl chloride was used implace of.2,4-di=tert.-amylphenoxyacetylchloride. It. melted at 59-61? 7 Anal. calcd. for C5 H N O C, 73.1; H, 10.2; N,..718. Found: 0.73.4; l-l,10.1;N,'7.7.

Coupler" No. 8

usual manner.v

The benzoylacetvo alkoxyanilide couplers with which the couplers of "the present invention are particularlyfusefulare described in the McCrossen, et al.,..U.-' S. patent application Serial No.'575,099," filedMarch 30, 1956, and have. the following general formula:

wherein R represents "an; alkyl' group of fr'om'l to. 30 carbonatoms. and one of the groups X and Y represents a hydrogen atom" and' the other represents an acylamido group.

A'particular groupofth'ese benzoylacet-o-allroxyanilide couplers efiicacious for use with the above couplers ofthe' invention have the above general formula:.wherein R represents "an 'alkyl' group of from about :1 to .20 carbon. atoms andone of the" groups X' a1'1d' Y' represents a .hy, drogen'" atom" and 'the' other represents :the 'group wherein R represents .eith'era hydrogenatom or analkyl group. of vfromnabout 1 tot4 carbon atoms.

a {3' [it (2,4- di 11 amylphenoxy)butyramidol fbenzoyl}- 2- methoxyacetanili'de 3 benzoylacetamino 4 methoxy (2',4' di tert.

amylphenoxy) acetanilide a {3 [or (2,4 di tert. amylphenoxy)acetamido] benzoyl} 2' methoxyacetanilide a {3 [a (2,4 di tert. amylphenoxy)butyramido1 benzoyl} 2 methoxyacetanilide a benzoyl 5 [a (2,4 di tert. amylphenoxy); butyramido] 2'- methoxyacetanilide 0c {4 [d (2,4 di tert. amylphen0xy.)'acetamido]-j benzoyl} 2 --methoxyacetanilide The couple'rs' ofthe invention are particularly useful with the above benzoylacet-o-alkoxyanilide couplers'be cause-=theabsorptionmaxi'ma of the" lemon-yellow "dyes obtained from the latter are-"shifted "somewhat towardthe shorter wavelength of the spectrum, the" absorption maxima being-at about 445 "millimicrons; resulting 1111""311 appreciable gap in absorption betweenthe yellow dye "and the usual magenta 'dyes obtained in"'color development. As mentioned, the absorption maxima of typical dyes obtained from couplers No. 1 to 8 coupled with 2-amino-5- diethylaminotoluene hydrochloride in the color development reaction are given above opposite each structural formula. Therefore, since the couplers of the present invention have a somewhat broader absorption and the absorption maxima are at Wavelengths in the range of 515-524 millimicrons, the gap in absorption is materially closed and the color films containing the two types of couplers more faithfully reproduce scenes in natural color.

The coupler compounds of the invention find usage in a wide variety of photographic color processes particularly wherein the couplers are dispersed in an emulsion layer such as a gelatino silver halide emulsion layer by'means of coupler solvents including cellulose esters, natural and synthetic resins and organic crystalloidal materials having a'hoiling point above .about170 C., as describedin the Mannes et al. U. S. Patent 2,304,940, granted December 15, 1942, and the Jelley et al. U. S. Patent 2,322,027, granted June 15, 1943. The optimum quantity of coupler to use in the emulsion layer can be determined by simple experiment and will depend somewhat upon the coupling activity of the particular coupler, the silver halide content of the emulsion layer, the particular process in which I the emulsion is to be used and other factors well known in the art of emulsion making.

In multilayer color films wherein the couplers of the invention are particularly useful, the couplers are preferably present in a green-sensitive emulsion layer and the mentioned benzoylacet-o-alkoxyanilide couplers may be present in-the overlying blue-sensitive emulsion layer, a yellow filter layer intervening. A cyan coupler may then be present in the lower red-sensitive emulsion layer adjacent to the green-sensitive emulsion layer.

After exposure of the multilayer color films containing the couplers of the invention, development may be carried out by the usual methods either to obtain a color negative directly'or color development may be carried out indirectly by reversal methods to obtain a color positive. A suitable color developing solution for this purpose is as follows:

Grams Z-amino-S-diethylaminotoluene HCl 2 Sodium sulfite (anhydrous) 2 Sodium carbonate (anhydrous) 20 Potassium brnmirle 1 Water to 1 liter.

In the development of' exposed photographic silver halide emulsion layers, using the couplers of our invention, any color forming developer containing a primary amino group may be used. These-include developers having two primary amino groups as well as those having one of the amino groups substituted or having substituents in the ring such as alkyl phenylenediamines and alkyl toluylene di-- amines. These compounds are usualy used in the salt formsuch as the hydrochloride or the sulfate which are more stable than the amines themselves. Suitable compounds are diethyl-p phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethylp-phenylenediamine hydrochloride and Z-amino-S-diethylaminotoluene hydrochloride. The p-amino phenols and their substitution products may also be used where the amino group is unsubstituted. All of these developers have an unsubstituted amino group which enables the oxidation products of the developer to couple with the color forming compounds to form a dye image. The N- alkylsultonamido alkyl-p-phenylenediamines of U. S. Patent 2,193,015 are particularly useful as color-forming developing agents. v

The development process may be employed for the production of colored photographic images in layers of gelatin or other carriers, such as collodion, organic esters ofcellulose, or synthetic resins. The carrier may be supported by a transparent medium such as glass, a cellulose ester or a nontransparent reflecting medium such as paperor an opaque cellulose ester. The emulsion may be coatedas a single layer on the support or as superposed layers on one or both sides of the support.

The silver halide component of the emulsion layers is not especially critical and may be, for example, silver bromoiodide, silver bromide or silver chloride, etc., depending upon the results desired. Likewise,the emulsions which are developed in the presence of the novel couplers may consist of single-layer or differentially sensitized multilayer films.

The examples and compounds set forth in the present specification are illustrative only and it is to be taken as limited only by the scope of the appended claims.

What we claim is:

l. A photographic silver halide emulsion containing a coupler compound having the general structure wherein R represents an alkyl group of from 1 to 12 carbon atoms, R represents a monocyclic aryl group of the benzene series, n represents a positive integer of from 1 to 2, n represents a positive integer of from 1 to 3, R repre sents a member of the class consisting of a hydrogen atomand a lower alkyl group and m represents a positive integer from 1 to 2.

2. A photographic silver halide emulsion containing a coupler compound ofthe class consisting of 1 methyl 3 [a {4 [a (2,4 di tert. amylphenoxy)butyramido]phenoxy}acetamido] 5 pyrazolone; 1 methyl 3 [a {4 [0; (2,4 di tert. amylpheuoxy)acetamido]phenoxy}acetamido] 5 pyrazolone; 1 methyl 3 {4 [a (2,4 di tert. amylphenoxy)acetamido] phenoxy} butyramido] 5 pyrazolone; 1 dodecyl 3 [or (2,4 di tert. amylphenoxy) acetamido] 5 pyrazolone; 1 hexyl 3 [a (2,4 di n amylphenoxy)acetamido] 5 pyrazolone; 1 hexyl 3 [a {p [a (2,4 di tert. amylphenoxy) acetamido]- phenoxy}acetamido] 5 pyrazolone; 1 dodecyl 3 [a (2,4 di n amylphenoxy)acetamido] 5 pyrazolone; and 1 dodecyl 3 {m [u (2,4 di n amylphenoxy)- acetamido] benzamido} 5 pyrazolone.

3. A multilayer color film comprising a support having thereon the silver halide emulsion layer of claim 1 sensitiveto green light and a silver halide emulsion layer sensitive to blue light containing a coupler compound having the general formula thereon the silver halide emulsion layer of claim 1 sensitive to green light and a silver halide emulsion sensitive to blue light containing a coupler compound having the general formula x Y 6-00 onto 01mg wherein R represents an alkyl group of from 1 to 20 carbon atoms and one of the groups X and Y represents a hydrogen atom and the other represents the group a hydrogen atom and an alk bon atoms.

(IJIHH yl group of from 1 to 4 car- 10 References Cited in the file of this patent UNITED STATES PATENTS 2,511,231 Weissberger et a1 June 13, 1950 2,600,788 Loria et a1 June 17, 1952 2,721,798 Loria et a1 Oct. 25, 1955 FOREIGN PATENTS 1,070,244 France Feb. 17, 1954 

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING A COUPLER COMPOUND HAVING THE GENERAL STRUCTURE 